CN103769205B - A kind of preparation method of the composite catalyst for oil-containing micro-algae hydrothermal liquefaction - Google Patents
A kind of preparation method of the composite catalyst for oil-containing micro-algae hydrothermal liquefaction Download PDFInfo
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Abstract
The present invention relates to a kind of preparation method of the micropore-mesopore composite catalyst for oil-containing micro-algae hydrothermal liquefaction, this catalyst adopts that natural zeolite or kaolin and natural zeolite are aluminium source, inorganic silicon is silicon source, NaOH is alkali source, softex kw (CTAB) is template, dilute sulfuric acid adjust ph, then through step preparations such as overaging, crystallization, oven dry roastings.First aluminium source is added NaOH to dissolve, add a small amount of silicon source, add template, add remaining silicon source after strong stirring and react a period of time, in aged at room temperature 2-5h, crystallization 64-72h under loading crystallizing kettle uniform temperature, filtration washing, under air atmosphere, namely high-temperature roasting obtains this micropore-mesopore composite catalyst.Cheaper starting materials of the present invention, preparation method is simple, and the hydrothermal liquefaction for oil-containing micro-algae reacts, under 260-300 DEG C of condition, compared with on-catalytic hydrothermal liquefaction, bio oil productive rate improves more than 15%, bio oil calorific value improves more than 30%, is a kind of micro-algae subcritical water thermally liquefy catalyst of excellence.
Description
Technical field
The present invention relates to a kind of preparation method of catalyst, be specifically related to a kind of preparation method of oil-containing micro-algae subcritical water thermally liquefy micropore-mesopore composite catalyst.
Background technology
Whole world fossil energy is gradually exhausted, and environmental pollution increasingly sharpens, and micro-algae (Microalgae) has the features such as photosynthetic efficiency is high, adaptive capacity to environment is strong, growth cycle is short, do not occupy cultivated land, and micro-algae can utilize the CO in air or coal-fired flue-gas
2or growth also realizes sewage purification in sewage simultaneously; there is certain environment " reparation " ability; therefore; relative to the second generation lignocellulose-like biomass energy, micro-algae is converted into biology (former) oil (Biocrude, Bio-oil); can reach the object of production of energy and environmental protection, be a kind of " the environment increment energy " simultaneously.The third generation bio-fuel technology that bio oil is mark, the main direction of studying that will be nearly 5-10 biomass energy is prepared with micro-algae.
The bio oil by the method for thermochemical study (comprising pyrolysis, liquefaction, gasification etc.) algae being become high-energy-density is the effective way that biomass energyization utilizes, wherein, hydrothermal liquefaction (hydrothermalliquefaction, HTL) technology utilizes water to promote temperature and pressure, prepare micro-algae crude oil and there is following advantage: (1), without the need to through the high dry run of energy consumption, directly can utilize micro-algae raw material of high humility; (2) without the need to algae oil (lipid) extraction step, realize full algae trans-utilization, this technology is particularly useful for preparing bio-crude oil by micro-algae of low fat content, improves its gross energy utilization ratio; (3) comparatively pyrolytic reaction is gentle for reaction condition, and micro-algae hydrothermal liquefaction reaction temperature 240-350 DEG C, pressure 5 – 15MPa, consersion unit material requirements is low, and energy consumption of reaction is low.
Utilizing HTL technology to prepare micro-algae bio-crude oil is the intensive process of a class energy, compared with the micro-algae of raw material or micro-algae pyrolysis oil, liquefaction bio-crude oil has higher calorific value and lower oxygen content, but containing compositions such as acid, ketone, phenol, ester classes in the bio oil of post liquefaction, nitrogen content is higher simultaneously, therefore needs to remove just O, N as high-quality energy source use through further upgrading modification.If in full algae direct liquefaction reaction bio oil processed, add the heterogeneous catalyst that can use good hydrothermal stability in the liquefaction process of water or organic solvent, to reduce liquefaction reaction temperature, generation high yield, high heating value, viscosity are relatively little, the high-quality biological oil of good stability.
Summary of the invention
Higher for condensing temperature in above-mentioned micro-algae hydrothermal liquefaction process, the problems such as product bio oil oxygen, nitrogen content are high, the object of the present invention is to provide that a kind of cheaper starting materials is easy to get, preparation method be simple, after regeneration activation recovering good and can meet preferably the reaction of micro-algae hydrothermal liquefaction to the requirement of catalyst hydrothermal stability, acid site intensity and pore structure composite microporous-preparation method of mesoporous catalyst, with ensure realize subcritical water thermally liquefy condition under prepare hypoxemia, low nitrogen high-quality biological oil.
Preparation method of the present invention, that the mixture of metakaolin and the natural zeolite obtained with the natural zeolite of cheapness or kaolin roasting is for aluminium source, adopt NaOH to carry out the hydrolysis in aluminium source, add silicon source and template synthesizes through hydrothermal crystallization method, synthesized catalyst has suitable acid strength and pore structure.
Concrete steps of the present invention are as follows:
By a certain amount of natural zeolite or kaolin and natural zeolite mass ratio 1:(5-10) mixture, alkali (as particle NaOH), a small amount of (10-20%wt) Na
2siO
4add in plastic containers, add a certain amount of water-soluble solution; Put into baking oven by after container closure, temperature is set to 90 DEG C, leave standstill dissolving 12h, more than strong stirring 0.5h and make it fully dissolve.
Dissolve a certain amount of CTAB, then the turbid liquid of natural zeolite after dissolving is added the some milliliters of CTAB solution, finally add hydrolysis remaining Na completely
2siO
4solution, after stirring 1h, regulates pH scope 9-11, leaves standstill aging 4h.
Move into jelly with in teflon-lined bullet formula reactor, be placed in baking oven, set temperature is 120 DEG C, crystallization 48-72h.
By crystallization product suction filtration, clean, after drying in oven moisture, be placed in roasting in Muffle furnace, be warming up to 300 DEG C from room temperature with the rate program of 5-10 DEG C/min, constant temperature 0.5h, continue to be warming up to 550 DEG C with the rate program of 10 DEG C/min, constant temperature 3h.
The present invention also comprises the step adopting nickel salt solution to carry out ion-exchange after high-temperature roasting, and described nickel solution can be nickelous sulfate, basic nickel carbonate, nickel chloride etc.
Kaolin used is the metakaolin that commodity kaolin obtains after 750 DEG C of roasting 2h.
In the present invention, aluminium source natural zeolite used is one or more in clinoptilolite, chabasie or modenite.
Catalyst obtained by the present invention also has the micropore-mesopore structure of Al-MCM-41 molecular sieve while keeping natural zeolite crystal formation.
By adjustment Si, Al, CTAB, H in the present invention
2the thing mass ratio of O is (50-100): (1-10): (15-25): 100, prepares that degree of crystallinity is high, the micropore-mesopore composite catalyst of good hydrothermal stability.
Hydrothermal liquefaction catalyst prepared by the present invention reacts for micro-algae subcritical water thermally liquefy, add algae powder, water and catalyst fines in the 100mL intermittent kettle reactor of laboratory, nitrogen rises to reaction temperature with certain heating rate after purging, keep 30-45min at such a temperature, room temperature is down in reactor cooling, takes out product oil and carry out property analysis.
Micropore-mesopore composite catalyst prepared by the present invention is a kind of micro-algae subcritical water thermally liquefy catalyst of excellence.Raw materials used cheap and easy to get, the preparation method of micropore-mesopore composite catalyst of the present invention is simple, activation recovering is good and can meet the requirement of micro-algae hydrothermal liquefaction reaction to catalyst pore structure and acid site intensity preferably after regeneration.Use micro-algae subcritical water thermally liquefy technique of this catalyst that micro-algae bio oil can be made without the separating step of algae oil extraction, direct catalytic conversion prepares the high-quality biological oil of hypoxemia, low nitrogen; Products obtained therefrom bio oil has that yield is high, calorific value is high, and oxygen content is low simultaneously, nitrogen content is low, the advantage that acid number is low.The catalyst of inactivation through coke-burning regeneration, can be applied to the technique that micro-algae hydrothermal liquefaction is energy-conserving and environment-protective.
Accompanying drawing explanation
Fig. 1 is pH=10, Si/Al=100, and clinoptilolite is the little angle (a) of clin/MCM-41-10 and wide-angle (b) the XRD diffraction spectrogram of the synthesis of aluminium source.
Fig. 2 is pH=11, Si/Al=100, and clinoptilolite is the Ni ion-exchange of clin/MCM-41-11 of aluminium source synthesis, the little angle (a) of calcined catalyst and wide-angle (b) XRD diffraction spectrogram.
Detailed description of the invention
The present invention is further illustrated by specific embodiment below in conjunction with accompanying drawing.
Embodiment 1
By 200 object clinoptilolite 5.0g, Na
2sO
43.0g, NaOH(particle) 2.0g adds in plastic containers, adds the water-soluble solution of 50mL.Put into baking oven by after container closure, temperature is set to 90 DEG C, leave standstill and dissolve 12h.Dissolving a certain amount of CTAB, then by adding the CTAB solution 15mL of 0.01mol/L in the turbid liquid of clinoptilolite after dissolving, finally adding Na
2sO
420.0g is hydrolyzed solution 10mL completely, after stirring 1h, regulates pH to 10, leaves standstill aging 4h.Move into jelly with in teflon-lined bullet formula reactor, be placed in baking oven, set temperature is 120 DEG C, crystallization 72h.Crystallization product filtration washing, after under air atmosphere, Muffle furnace Program is warming up to 500 DEG C, constant temperature calcining 2h obtains clin/MCM-41-10 catalyst.The XRD spectra of clin/MCM-41-10 catalyst is shown in Fig. 1, maintains the monoclinic typical diffractive peak of clinoptilolite in wide angular range, has occurred the characteristic peak of MCM-41 in small angle range simultaneously.
Adopt clin/MCM-41-10 catalyst to carry out Laboratory batch still chlorella hydrothermal liquefaction and prepare bio oil activity rating.Algae powder 10.0g, catalyst 0.5g and 50mL water are added reactor, 260 DEG C, self-pressure, reaction 30min, the viscosity that product bio oil is 20 DEG C is 8300cP, and bio oil productive rate is 71.8%.Liquefy with on-catalytic and the product oil phase ratio of using natural clinoptilolite clin-c catalytic liquefaction, the product oil yield of clin/MCM-41-10 catalytic liquefaction and calorific value all increase (see table 1), this is because " accessibility " at the active acid center of hydrothermal liquefaction reaction on micropore-mesopore composite catalyst is far above microporous catalyst, therefore shows excellent liquefying activity.Meanwhile, the nitrogen content of the liquiefied product oil of clin/MCM-41 catalyst is also lower than clin-c catalyst.
The yield of table 1 chlorella and hydrothermal liquefaction product bio oil, elementary analysis and calorific value
| Bio oil yield (%) | C(%) | H(%) | N(%) | O(%) | Calorific value (MJ/kg) | |
| Chlorella | / | 49.25 | 7.07 | 9.15 | 34.53 | 20.64 |
| Hydrothermal liquefaction bio oil (catalyst-free) | 60.4 | 57.25 | 8.20 | 9.72 | 24.83 | 26.61 |
| Hydro-thermal catalytic liquefaction bio oil (Clin-c) | 69.8 | 61.14 | 8.50 | 9.49 | 20.87 | 29.06 |
| Hydro-thermal catalytic liquefaction bio oil (Clin/MCM-41-10) | 71.8 | 63.32 | 8.43 | 8.87 | 19.38 | 29.96 |
Embodiment 2-5
Raw material is 5 parts and embodiment 1 same materials, prepares according to the method identical with embodiment 1.They in aluminium source, template, all silicon source added under rear adjust ph is respectively 9.0,9.5,10.5,11.0 conditions and prepared, then leave standstill aging, crystallization, filtration washing, dry, high-temperature roasting obtains.Algae powder 10.0g, catalyst 0.5g and 50mL water are added reactor, 260 DEG C, self-pressure, reaction 30min, it prepares pH value and bio oil yield data in table 2.Clin/MCM-41 catalyst bio oil yield obtained when result shows that preparing pH value is 10.5 is the highest.
The yield of table 2 chlorella hydrothermal liquefaction product bio oil
| Catalyst sequence number | 1 | 2 | 3 | 4 |
| pH | 9 | 9.5 | 10.5 | 11 |
| Bio oil yield (%) | 71.4 | 71.9 | 72.8 | 71.2 |
Embodiment 6
The metakaolin 0.8g obtained after kaolin roasting being dissolved in the NaOH solution of 1.5mol/L, by 200 object clinoptilolite 5.0g and NaOH(particle) 3.0g adds in plastic containers, add the water-soluble solution of 100mL, 90 DEG C of baking ovens will be put into after container closure, leave standstill and dissolve 12h.Dissolving CTAB, then by adding the CTAB solution 15mL of 0.02mol/L in the turbid liquid in aluminium source after dissolving, finally adding 35.0gNa
2sO
4be hydrolyzed solution 35mL completely, after stirring 1h, regulate pH to 11, leave standstill aging 4h.Move into jelly with in teflon-lined bullet formula reactor, be placed in baking oven, set temperature is 120 DEG C, crystallization 72h.Crystallization product filtration washing, constant temperature calcining 2h after Muffle furnace Program is warming up to 500 DEG C under air atmosphere.Add the NiSO of 0.5mol/L
4solution carries out ion-exchange, filtration washing, dries roasting, obtained Ni-clin/MCM-41-11 catalyst.The XRD spectra of Ni-clin/MCM-41-11 catalyst is shown in Fig. 2, maintains the monoclinic typical diffractive peak of clinoptilolite in wide angular range, has occurred the characteristic peak of MCM-41 in small angle range simultaneously, and the characteristic peak that there is no NiO occurs.
Ni-clin/MCM-41-11 catalyst is adopted to carry out the experiment of chlorella hydrothermal liquefaction.Algae powder 10.0g, catalyst 0.5g and 50mL water are added reactor, 260 DEG C, self-pressure, reaction 30min, Ni-clin/MCM-41-11 catalytic liquefaction product oil yield be 76.0%, show good liquefying activity.
Embodiment 7-10
Raw material is 5 parts of raw materials identical with embodiment 6, prepares according to the method identical with embodiment 6.Add 0.25 respectively, 1.0,1.5, the NiSO of 2.0mol/L
4solution carries out ion-exchange, filtration washing, dries roasting, obtained catalyst.The yield of its ion-exchange concentration and chlorella hydrothermal liquefaction product bio oil is in table 3.Result shows Ni
2+ion-exchange concentration no longer increases more than liquiefied product oil yield after 1.5mol/L.
The yield of table 3 chlorella hydrothermal liquefaction product bio oil
| Catalyst sequence number | 1 | 2 | 3 | 4 |
| Ni 2+Ion-exchange concentration | 0.25 | 1.0 | 1.5 | 2.0 |
| Bio oil yield (%) | 74.7 | 76.8 | 78.4 | 77.2 |
Claims (8)
1. for a preparation method for the composite catalyst of oil-containing micro-algae hydrothermal liquefaction, it is characterized in that with natural zeolite being aluminium source, be template with softex kw, synthesize in the basic conditions; Concrete steps are as follows: first natural zeolite is added alkali and dissolve, add the silicon source of 10-20%wt, regulate pH>12, then add template softex kw, add remaining silicon source, make Si, Al, CTAB, H after strong stirring
2the thing mass ratio of O is (50-100): (1-10): (15-25): 100; Then be 9-11 by diluted acid adjust ph, then prepare described composite catalyst through overaging, crystallization, washing and filtering, oven dry, high-temperature roasting.
2. the preparation method of composite catalyst according to claim 1, is characterized in that described aluminium source also comprises kaolin.
3. the preparation method of composite catalyst according to claim 2, is characterized in that aluminium source kaolin used is the metakaolin that commodity kaolin obtains after 750 DEG C of roasting 2h.
4. the preparation method of composite catalyst according to Claims 2 or 3, it is characterized in that the step forming aluminium source colloidal sol is: mixed with the natural zeolite of pulverizing by the kaolin after calcining, its mass ratio is 1:(5-10), add NaOH solution to dissolve, regulate pH>12, more than strong stirring 0.5h.
5. the preparation method of composite catalyst according to claim 1, is characterized in that the step forming silicon source colloidal sol is: by Na
2siO
4use water-soluble solution, more than strong stirring 0.5h.
6. the preparation method of composite catalyst according to claim 1, it is characterized in that the step of high-temperature roasting is: be warming up to 300 DEG C from room temperature with the rate program of 5-10 DEG C/min, constant temperature 0.5h, continues to be warming up to 550 DEG C with the rate program of 10 DEG C/min, constant temperature 3h.
7. the preparation method of composite catalyst according to claim 1, also comprises the step adopting nickel salt solution to carry out ion-exchange after it is characterized in that high-temperature roasting.
8. the preparation method of composite catalyst according to claim 1, is characterized in that aluminium source natural zeolite used is one or more in clinoptilolite, chabasie or modenite.
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| CN105772076B (en) * | 2016-02-29 | 2018-05-15 | 清华大学 | A kind of mesoporous catalyst with hydrothermal stability, its preparation method and the method for preparing bio oil with its catalysis hydrothermal liquefaction microalgae |
| CN108300565A (en) * | 2017-12-20 | 2018-07-20 | 湖北工业大学 | A method of it is mixed fatty acid extracted from the wet algal gel of microalgae using subcritical water |
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